Sulfo group-free polyazo compounds containing at least two basic water-solubilizing groups in metal-free or metal complex form

ABSTRACT

Metal-free compounds and 1:1 and 1:2 metal complexes of the formula ##STR1## or a 1:2 metal complex of a metal-free compound of said formula and a metallizable azo compound not of said formula, wherein 
     each K is independently a coupling component radical of the pyrazolone-5, 5-aminopyrazole, pyridone, 2,6-diaminopyridine, β-naphthol, acetic acid ester, acetic acid amide or N-substituted N,N-disubstituted aniline series, 
     each K 1  is independently ##STR2##  wherein R 3  is hydrogen, C 1-4  alkyl, phenyl or benzyl, 
     R 4  is C 1-4  alkyl, (C 1-4  alkoxy)-carbonyl or --CO--N(R 8 ) 2 , wherein each R 8  is independently hydrogen or C 1-4  alkyl, 
     R 5  is amino or hydroxy, 
     R 5a  is hydroxy, 
     T is hydrogen, cyano, ##STR3##  or (C 1-4  alkyl)carbonyl, wherein R 7 , R 10 , R 12 , Z a  and A⊖ are as defined in the specification, 
     each R 1  is independently hydrogen, halo, hydroxy, C 1-4  alkoxy or C 1-4  alkyl, or 
     R 1  and R 5 , located on rings attached to the same azo radical, are --O--Me--NH or --O--Me--O--, wherein Me is a 1:1 or 1:2 metal complex-forming metal ion, or 
     R 1  and R 5a , located on rings attached to the same azo radical, are --O--Me--O--, wherein Me is as defined above, 
     each R 2  is independently hydrogen, halo, C 1-4  alkyl or C 1-4  alkoxy, 
     X is a direct bond or a bridging radical as defined in the specification, and 
     each q is independently 0 or 1, 
     with the provisos that (i) the compound of Formula I has at least two basic water-solubilizing groups, and (ii) each end of X is in a 3- or 4-position of the Ring A to which it is attached, which metal-free compounds and 1:1 and 1:2 metal complexes are useful as dyes, particularly for paper and leather.

The invention relates to sulpho group-free azo compounds in metal-freeor metallised form, which are useful as dyestuffs.

According to the invention there is provided compounds which inmetal-free form are of formula I ##STR4## in which

each K independently is the residue of a coupling component of thepyrazolone-5 series,

the 5-aminopyrazole series, the pyridone series, the β-naphthol series,the 2,6-diaminopyridine series, the acetic acid ester series or aceticacid amide series or N-substituted or N,N-disubstituted aniline series;

each R₁ independently is selected from hydrogen, halogen, hydroxy,unsubstituted C₁₋₄ alkoxy and unsubstituted C₁₋₄ alkyl,

each R₂ independently is selected from hydrogen, halogen, unsubstitutedC₁₋₄ alkyl and unsubstituted C₁₋₄ alkoxy;

each q independently is 0 or 1;

each K₁ independently is selected from a group of formula II or formulaIII ##STR5## in which

the starred atom is attached to the phenyl group;

each R₃ independently is selected from hydrogen, unsubstituted C₁₋₄alkyl, unsubstituted phenyl and unsubstituted benzyl;

each R₄ independently is selected from unsubstituted C₁₋₄ alkyl and--CO--R₆ ;

each R₅ independently is --NH₂ or --OH and each R_(5a) is --OH;

each R₆ independently is C₁₋₄ alkoxy or --N(R₈)₂ ;

each R₈ independently is hydrogen or unsubstituted C₁₋₄ alkyl;

each T independently is hydrogen, --CN, ##STR6## where

R₇ is unsubstituted C₁₋₄ alkyl;

each R₁₀ independently is hydrogen, --N(R₁₂)₂, --CON(R₁₂)₂ orunsubstituted C₁₋₄ alkyl;

each Z_(a) independently is --S--, --O-- or ##STR7##

each R₁₂ independently is hydrogen, unsubstituted cyclohexyl or C₁₋₄alkyl unsubstituted or substituted by one --OH group;

A.sup.⊖ is a non-chromophoric anion;

X, when both R₁ 's are hydrogen, is X₁ to X₇₃ ;

X₁ a direct bond,

X₂ a linear or branched unsubstituted C₁₋₄ alkylene group, ##STR8## or,

X, when one R₁ is other than hydrogen, is X₁, X₂, X₁₄, X₂₁, X₃₂ or X₃₄,

where R₁₄ is halogen, unsubstituted C₁₋₄ alkyl and unsubstituted C₁₋₄alkoxy;

each R₁₅ independently is selected from hydrogen or unsubstituted C₁₋₄alkyl;

R₁₆ is selected from halogen, --OH, --NH₂, an aliphatic amine group, anaromatic amine group and a cycloaliphatic amine group;

each R₁₇ independently is a linear or branched unsubstituted C₁₋₄alkylene group;

each g independently is an integer from 1 to 4 inclusive;

or when the compounds of formula I are in 1:1 or 1:2 metal complex form,R₁ and R₅ (located on rings attached to the same azo group) form a group--O--Me--NH-- or --O--Me--O-- or R₁ and R_(5a) (located on ringsattached to the same azo group) form a group --O--Me--O--, where Me is a1:1 or 1:2 complex-forming metal atom;

with the provisos:

(i) that the compounds of formula I have at least two basicwater-solubilising groups; and

(ii) that X is attached in the 3- or 4-position of the phenyl ring.

The term "basic water-solubilising group" includes cationic groups andprotonatable basic groups. Hence the minimum requirement for twowater-solubilising basic groups may be made up of a cationic and aprotonatable basic group or two protonatable basic groups or twocationic groups.

In this specification, unless indicated to the contrary, thesignificances of any symbol appearing more than once in a formula areindependent of one another.

Preferably any halogen is chloro or bromo, more preferably the former;preferably any C₁₋₄ alkyl is methyl or ethyl and preferably any C₁₋₄alkoxy is methoxy or ethoxy.

Preferably Me is iron, copper, cobalt, nickel, manganese or chromium in1:1 metal complexes. Preferably Me is cobalt, chromium, nickel or ironin 1:2 metal complexes. More preferably Me is copper in 1:1 metalcomplexes and cobalt, chromium or iron in 1:2 metal complexes.

For the avoidance of doubt in 1:2 metal complexes according to theinvention it is only necessary for one of the complexing azo compoundsto be of formula I. The other complexing unit may or may not be aresidue of a metal-free compound of formula I.

Preferably however both complexing units are residues of a metal-freecompound of formula I. More preferably compounds of formula I aresymmetric.

Preferred compounds of formula I are of formula I' ##STR9##

in metal-free or 1:1 or 1:2 metal complex form;

in which each K₁ ' independently is selected from groups of formulae II'and III' ##STR10## in which

the starred atom is attached to the phenyl ring;

R₁ ' is hydrogen, Cl, methyl, methoxy or --OH, R₅ is --NH₂ or --OH andR_(5a) is --OH; or R₁ ' and R₅ form a group --O--Me--O-- or --O--Me--NH;or R₁ ' and R_(5a) form a group --O--Me--O--;

R₃ ' is --CH₃, --C₂ H₅ or unsubstituted phenyl;

T' is hydrogen, --CN, --CONH₂ or ##STR11## where

R₁₀ ' is hydrogen, methyl, --NH₂, --N(CH₃)₂ or --CONH₂ ;

K' is a group of formulae Ka to Kg ##STR12## in which

R₁₈ is hydrogen, unsubstituted C₁₋₄ alkyl, ##STR13##

R₁₉ is hydrogen, unsubstituted C₁₋₆ alkyl, ##STR14## where

m is an integer from 1 to 6 inclusive;

n is an integer from 1 to 4 inclusive;

R₂₁ is hydrogen, C₁₋₄ alkyl unsubstituted or monosubstituted by alkoxy(e.g., methoxy), --(CH₂)₂ OH or (CH₂)₂₋₃ --Z;

R₂₂ is --NH(CH₂)_(m) --Z or ##STR15##

Z₁ is --N(R₂₉)₂, --N.sup.⊕ (R₃₀)₂ R₃₁ A.sup.⊖ or --OH;

Z is a group --N(R₂₉)₂ or --N.sup.⊕ (R₃₀)₂ R₃₁ A.sup.⊖ ;

V is a linear C₁₋₁₂ alkylene or C₃₋₁₂ alkenylene group, the alkylene oralkenylene group of which may be interrupted by 1 or 2 heteroatoms(preferably Z_(a) defined above);

R₂₄ is hydrogen, halogen, unsubstituted C₁₋₄ alkyl, unsubstituted C₁₋₄alkoxy, --NO₂, --NH₂ or --NHCOCH₃ ;

R₂₅ is hydrogen, --NHCO(CH₂)₁₋₂ --Z, --SO₂ NH(CH₂)₂₋₃ --Z or ##STR16##

R₂₇ is hydrogen, --NH₂, --NHCH₃, --N(CH₃)₂, --N(C₂ H₅)₂, --NHCOCH₃,--NH--CO(CH₂)₁₋₂ --Z, ##STR17##

R₂₈ is halogen, --OH, --NH₂, --NHC₂ H₄ OH, --N(C₂ H₄ OH)₂, ##STR18##

each R₂₉ independently is hydrogen, C₁₋₄ alkyl unsubstituted ormonosubstituted by a phenyl group or C₂₋₄ alkyl monosubstituted by --OH,halogen or --CN or both R₂₉ 's together with the N atom to which theyare attached form an unsubstituted morpholine, piperidine, pyrrolidine,piperazine or N-methylpiperazine ring;

each R₃₀ independently has a significance of R₂₉ (independently of R₂₉)other than hydrogen and R₃₁ is C₁₋₄ alkyl, unsubstituted or substitutedby a phenyl group or both R₃₀ 's and R₃₁ together with the N-atom towhich they are attached form an unsubstituted pyridine, picoline orlutidine ring or ##STR19##

V₁ is linear unsubstituted C₁₋₄ alkylene;

R₃₂ is hydrogen, --V₁ --Z, or C₁₋₄ alkyl unsubstituted ormonosubstituted by --OH;

R₃₃ is hydrogen, unsubstituted C₁₋₄ alkyl, --NHCOR₇ or --NHCO--V₁ --Z,where R₇ is C₁₋₄ alkyl;

X', when both R₁ ' s are hydrogen, is X₁, X₅, X₆, X₇, X₁₀, X₁₁, X₁₂,X₁₆, X₁₇, X₂₂, X₂₅, X₂₆, X₂₇, X₃₀, X₃₁, X₄₉, X₅₀, X₅₁, X₅₂, X₅₃, X₅₄,X₅₈, X₅₉, X₆₄, X₇₂ or, ##STR20## wherein

R_(14a) is hydrogen, Cl, --CH₃ or --OCH₃ ; and

R_(16a) is Cl, --OH, --NH₂, --NH--CH₂ CH₂ --OH, --NH(CH₂)₃ N(C₂ H₅)₂,--N(CH₂ --CH₂ OH)₂, ##STR21##

X', when one R₁ ' is other than hydrogen, is selected from X₁, X₂ ', X₂", X₁₄ ', X₂₁ ', X₃₂ " and X₃₄ ';

with the provisos:

(i) that the azo group is in a 3- or 4-position of ring B;

(ii) that X' is attached in a 3- or 4-position to each phenyl ring; and

(iii) that in the compound of formula I' there are at least twowater-solubilising basic groups present.

More preferred compounds of formula I are of formula I" ##STR22## inmetal-free or 1:1 or 1:2 metal complex form, in which K₁ " is of formulaII" or III' ##STR23## where

the starred atom is attached to the phenyl ring;

R₁ ' is hydrogen, Cl, methyl, methoxy or --OH, R₅ is --OH or --NH₂ andR_(5a) is --OH or R₁ ' and R₅ form a group --O--Me₁ --NH-- or --O--Me₁--O-- or R₁ ' and R_(5a) form a group --O--Me₁ --O--, where Me₁ iscopper for 1:1 metal complexes and cobalt, chromium or iron for 1:2metal complexes;

T" is --CN or ##STR24##

R₁₀ " is hydrogen, methyl or --NH₂

K" is a group of one of the formulae Ka' to Kg' ##STR25## wherein

R₁₈ ' is hydrogen, ##STR26##

R₁₉ ' is hydrogen, methyl, ethyl, benzyl, ##STR27## where

R₁₅ ' is hydrogen or methyl;

R₂₁ ' is hydrogen, methyl, ethyl, --(CH₂)₂ OH, --(CH₂)₃ --OCH₃, or--(CH₂)₂₋₃ --Z';

R₂₂ ' is --NH(CH₂)₂₋₃ --Z' or ##STR28##

R₂₄ ' is hydrogen, chloro, methyl, methoxy or --NHCOCH₃ ;

R₂₅ ' is hydrogen, --NHCOCH₂ --Z', --SO₂ NH(CH₂)₂₋₃ --Z'. or ##STR29##

R₂₇ ' is hydrogen, --NH₂, --N(CH₃)₂, --N(C₂ H₅)₂, --NHCOCH₃, --NHCOCH₂--Z', ##STR30## --(CH₂)₂₋₃ --Z' or --SO₂ NH(CH₂)₂₋₃ --Z';

R₂₈ ' is chloro, --OH, --NH₂, ##STR31## --NHC₂ H₄ OH, --N(C₂ H₄ OH)₂,--NHC₂ H₄ CN, --NH(CH₂)₃ OCH₃ or --NH--(CH₂)₂₋₃ --Z',

Z₁ ' is --N(R₂₉ ')₂ or --OH;

Z' is --N(R₂₉ ')₂ or --N.sup.⊕ (R₃₀ ')₂ R₃₁ 'A.sup.⊖ ;

V' is --(CH₂)_(b) -- where b is an integer from 2 to 6 inclusive;

R₂₉ ' independently is hydrogen, methyl or ethyl or both R₂₉ ' stogether with the N atom to which they are attached form anunsubstituted morpholine, piperidine, piperazine or N-methylpiperazinering;

each R₃₀ ' independently is methyl or ethyl and R₃₁ ' is methyl, ethylor benzyl or both R₃₀ ' s and R₃₁ ' together with the N atom to whichthey are attached form an unsubstituted pyridine ring or a α- orβ-picoline ring; and

R₃₃ ' is hydrogen, methyl, --NHCOCH₃, --NHCOC₂ H₅ or --NHCO(CH₂)₂₋₃--Z';

X", when both R₁ ' s are hydrogen, is X₁, X₁₁, X₁₇, X₂₇, X₅₁, X₅₂, X₅₄,X₆₄, X₇₂, X₂ ', X₂ ", X₁₄ ', X₁₉ ', X₁₉ ", X₁₉ '", X₂₀ ', X₂₀ ", X₃₂ ',X₃₂ ", X₃₄ ', X₃₄ ", X₃₄ '", X₃₄ ^(iv), X₃₄ ^(v), X³⁴ ^(vi), X₆₇ ' andX₆₈ '; and when one of R₁ ' is other than hydrogen, X" is a direct bond;

with the provisos:

(i) that in the compound of formula I" there are at least two basicwater-solubilising groups; and

(ii) that the azo group is in the 3- or 4-position of ring B.

In compounds according to the invention:

preferably q is 0;

preferably K₁ is K₁ ', more preferably K₁ ";

preferably R₁ is R₁ ';

preferably R₃ is R₃ ', more preferably CH₃ ;

preferably R₄ is CH₃ ;

preferably T is T', more preferably T";

preferably R₁₀ is R₁₀ ', more preferably R₁₀ ";

preferably R₁₂ is hydrogen or methyl, more preferably the latter;

preferably K is K', more preferably K";

preferably X is X', more preferably X";

preferably R₁₄ is R_(14a) ;

preferably R₁₅ is hydrogen or methyl;

preferably R₁₆ is R_(16a) ;

preferably g is 2, 3 or 4;

preferably R₁₇ is --(CH₂)₂₋₃ --.

preferably R₁₈ is R₁₈ ';

preferably R₁₉ is R₁₉ ';

preferably R₂₁ is R₂₁ ';

preferably R₂₂ is R₂₂ ';

preferably R₂₄ is R₂₄ ';

preferably R₂₅ is R₂₅ ';

preferably R₂₇ is R₂₇ ';

preferably R₂₈ is R₂₈ ';

preferably R₂₉ is R₂₉ ';

preferably R₃₀ is R₃₀ ';

preferably R₃₁ is R₃₁ ';

preferably R₃₃ is R₃₃ ';

preferably Z is Z';

preferably Z₁ is Z₁ ';

preferably V is V'; and

preferably V₁ is --(CH₂)₂₋₃.

R₁₆, when an aliphatic amine, is preferably of the formula ##STR32##where

R₃₄ is hydrogen or C₁₋₄ alkyl; R₃₅ is C₁₋₄ alkyl unsubstituted ormonosubstituted by --OH and A₁ is a linear or branched C₁₋₄ alkylene.More preferably R₁₆ when an aliphatic amine, is --NHCH₂ CH₂ OH, --N(CH₂CH₂ OH)₂ or --NH--(CH₂)₃ --N(C₂ H₅)₂ ;

R₁₆, when an aromatic amine, is preferably ##STR33## more preferably##STR34##

R₁₆, when a cycloaliphatic amine, is preferably ##STR35## morepreferably ##STR36##

R₁₉, when phenyl(C₁₋₃ alkyl), is preferably ##STR37##

R₁₉, when alkoxyalkyl, is preferably --(CH₂)₃ --OCH₃.

V, when an alkylene group, is preferably --(CH₂)₂ --.

R₂₈, when --NH--(CH₂)₂₋₃ --OC₁₋₄ alkyl, is preferably --NH(CH₂)₃ OCH₃.

R₃₀, when an alkyl group substituted by phenyl, is preferably benzyl.

Compounds of formula I in metal-free form may be prepared by reacting 1mole of a tetrazotised compound of formula VI ##STR38##

with the proviso that the --NH₂ group and X group are in the 3- or4-position on their respective phenyl rings

with 2 moles of a compound of formula VII

    H--K                                                       (VII)

The diazo coupling can be carried out according to known methods.Advantageously, coupling is carried out in aqueous, acid, neutral oralkali medium at a temperature from -10° C. to room temperature, ifnecessary in the presence of a coupling accelerator such as pyridine orurea. Alternatively, coupling may be effected in a mixture of solvents,for example water and an organic solvent.

The azo compounds of formula I in 1:1 metal complex form may be preparedby metallising compounds of formula I in metal-free form with a metalselected from copper, cobalt, iron, nickel, manganese, chromium andzinc.

The azo compounds of formula I in 1:2 metal complex form may be preparedby metallising compounds of formula I in metal-free form with metalselected from chromium, nickel, cobalt and iron.

A further method for the preparation of an azo compound of formula I in1:2 metal complex form is bonding an azo compound of formula I inmetal-free form (or a metallisable azo compound of a formula other thanformula I) with an azo compound of formula I in 1:1 metal complex formwhen the metal is chromium, nickel, cobalt or iron.

The metallisation process to form a 1:1 metal complex is advantageouslycarried out by treating 1 mole of azo compound with a metallising agentcontaining 1 equivalent of metal.

Metallisation is carried out by known methods, by metallising at a pHrange of preferably 2 to 7 with the metal salt or by oxidativelycoppering preferably at pH 4 to 7 in the presence of the copper salt andan oxidation agent (H₂ O₂, for example) or by demethylatively copperingor cobaltising preferably at pH 3 to 4 at a raised temperature in thepresence of a metal salt.

Advantageously, for instance, cobaltisation may be carried out in thepresence of an inorganic nitrite such as lithium, sodium, ammonium orpotassium nitrite in the ratio of 2 to 6 moles of nitrite per gram atomof cobalt.

Suitable cobalt-yielding compounds are, for example, cobalt (II) and Co(III) sulphate, acetate, formate or chloride.

Copper-yielding compounds are, for example, cupric sulphate, cupricformate, cupric acetate and cupric chloride.

Suitable nickel-yielding compounds are Ni(II) and Ni(III) compounds,such as nickel formate, nickel acetate and nickel sulphate.

Suitable manganese-yielding compounds are Mn(II) compounds andiron-yielding compounds are Fe(II) and Fe(III) compounds. Examples ofthese and zinc-yielding compounds are manganese, iron and zinc formate,acetate and sulphate.

Suitable chromium-yielding compounds are Cr(II) and Cr(III) formate,acetate and sulphate.

Compounds of formula VI are known or may be prepared by known methodsfrom known compounds.

Compounds of formula VII are known or may be made from known compoundsby known methods except when K is a group of formula Ke and Kg (definedunder K'). An example of the formation of a compound of formula VII whenK is a group of formula Kb and R₁₉ is a group --(CH₂)₂ --NH₂ (definedunder K') is given below.

A compound of the formula VIII ##STR39## where V' is --C₂ H₄ -- can beformed by the reaction of a paranitrobenzoic acid aryl ester withethylenediamine. The compound of formula VIII is then reacted withchloroacetic acid methyl ester and then with pyridine according to knownmethods to form a compound of formula IX ##STR40##

Acetoacetic acid methyl ester is added to the compound of formula IX at25° C. in the presence of NaOH causing it to cyclise to form a compoundof formula X ##STR41##

The compound of formula X can be saponified by the addition of 5 to 7%HCl to give an amine of formula XI ##STR42##

Compounds of formula VII in which K is Ke can be prepared by cyclising 2moles of a compound of the formula XIa

    Z.sub.1 --V--NHCOCH.sub.2 --CN                             (XIa)

for example in practically water-free organic solvent (such as analcohol) at elevated temperatures in the presence of a base (such as analcoholate). The compounds of formula XIa are known or may be preparedby known methods from known compounds.

Compounds of formula VII in which K is Kg (defined under K') can beprepared by reacting cyanoacetic ester with an amino alcohol and,without isolation of the cyanoacetic acid amide, cyclising at raisedtemperatures in the presence of a strong base, for example analcoholate.

The anion A.sup.⊖ may be any non-chromophoric anion which is usual inbasic dyestuff chemistry.

In the compounds of formula I, any anion A.sup.⊖ may be exchanged forany other non-chromophoric anion, e.g. with the aid of an ion exchanger,or by means of a reaction with salts or acids, optionally in severalstages, e.g. through the hydroxide or the bicarbonate, or in accordancewith German Published Specification No. 2,001,748 or 2,001,816.

The anion A.sup.⊖ includes both organic and inorganic ions, e.g. halide(such as chloride or bromide), sulphate, bisulphate, methylsulphate,aminosulphonate, perchlorate, benzenesulphonate, oxalate, maleinate,acetate, propionate, lactate, succinate, tartrate, malate,methanesulphonate and benzoate ions, complex anions (such as those ofzinc chloride double salts) and the anions of the following acids: boricacid, citric acid, glycolic acid, diglycolic acid and adipic acid, oraddition products of ortho-boric acid with polyalcohols, e.g.cis-polyols.

The compounds of formula I in quaternised form and/or in the form of thecorresponding salts of mineral acids or organic acids may be useddirectly as dyestuffs. They may be used in the form of aqueous stablesolutions or as granules and may be used for dyeing all types of fibrematerial, cellulose, cotton and leather, especially paper and paperproducts, and bast fibres, such as hemp, flax, sisal, jute, coir andstraw.

The compounds of formula I may also be employed in the production ofbulk-dyed, sized and unsized paper. They may be similarly employed fordyeing paper by dipping.

Paper, leather and cellulose are dyed in accordance with known methods.

In paper production, the compounds of formula I and their preparationsdo not colour the waste water at all, or only slightly which isparticularly useful for purifying waste water. Compounds of formula Iare highly substantive, do not give mottled dyeings when dyed on paper,and are substantially insensitive to pH. The dyeings on paper arenotable for their good light fastness properties. After long-termexposure to light, the shade alters tone-in-tone. The dyed papers arewetfast, not only to water, but also to milk, soap water, sodiumchloride solutions, fruit juices and sweetened mineral water, andbecause of their good alcohol fastness, they are also resistant toalcoholic beverages. Furthermore, when dyed on paper, they producedyeings having a very stable shade.

The compounds of formula I may be used for dyeing, padding or printingpolyacrylonitrile textiles, or polyamide or polyester textiles which aremodified by anionic groups.

In the following Examples, all parts and percentages are by weight andall temperatures are given in degrees Centigrade unless indicated to thecontrary.

EXAMPLE 1

15 Parts of N,N'-(bis-para-aminobenzoyl)ethylenediamine are suspended in150 parts of water and 25 parts of 10N hydrochloric acid. 25 Parts of a4N sodium nitrite solution are added over the course of 20 minutes at atemperature of between 0° and 5°. After the addition of the nitrite, theresidual nitrous acid is destroyed with aminosulphonic acid. Thediazonium salt solution formed is filtered by adding decolourisingcarbon.

This solution is then added dropwise over 30 minutes at 10° and 15° to acoupling solution containing hydrochloric acid, and 20 parts of1-(3'-aminophenyl)-3-methyl-5-hydroxypyrazole. During this addition, thepH value is kept at between 2.5 and 3.5 by adding simultaneously asolution of caustic soda. When coupling has ended, the reaction mixtureis rendered alkaline with ammonia solution, and the dyestuff suspensionis heated to 60°. After cooling, it is filtered and washed with water.The bisazo dyestuff thus obtained is suspended in hydrochloric acid, isbisdiazotised in a manner analogous to that described above using sodiumnitrite, and is coupled at a pH value of 2 to 3 with the couplingcomponent1-(3'-dimethylaminopropyl)-3-pyridinium-4-methyl-6-hydroxy-1,2-dihydropyrid-2-onechloride, which is in a slightly acidic solution containing hydrochloricacid. After coupling, the dyestuff is isolated by addition of ammoniaand filtering the resulting suspension. The dyestuff so obtained has theformula ##STR43## and when in a slightly acidic solution, dyes cotton,leather and paper yellow. The paper dyeings have good light fastness andvery good wet fastness.

In the following Tables the significances of X (i.e. as any one of X₁ toX₇₃) are as given earlier in the specification. ##STR44## wherein thestarred atom is bound to the ring G; ##STR45##

EXAMPLES 2 TO 145

Compounds of the formula ##STR46## wherein A, T, KI, X and G are definedin Table I, can be prepared by a method analogous to that of Example 1from appropriate starting materials.

                  TABLE I                                                         ______________________________________                                        EX.             Position of azo                                               No.     K       group on Ring G                                                                            T     A     X                                    ______________________________________                                        2       K.sub.2 3            T.sub. 1                                                                            A.sub.2                                                                             X.sub.34 '                           3       K.sub.2 3            T.sub.2                                                                             A.sub.3                                                                             "                                    4       K.sub.2 3            T.sub.1                                                                             A.sub.3                                                                             "                                    5       K.sub.2 3            T.sub.3                                                                             A.sub.3                                                                             "                                    6       K.sub.2 3            T.sub.4                                                                             A.sub.3                                                                             "                                    7       K.sub.2 3            T.sub.5                                                                             A.sub.3                                                                             "                                    8       K.sub.2 3            T.sub.6                                                                             A.sub.3                                                                             "                                    9       K.sub.2 3            T.sub.7                                                                             A.sub.3                                                                             "                                    10      K.sub.2 3            T.sub.1                                                                             A.sub.4                                                                             "                                    11      K.sub.2 3            T.sub.1                                                                             A.sub.5                                                                             "                                    12      K.sub.2 3            T.sub.1                                                                             A.sub.6                                                                             "                                    13      K.sub.2 3            T.sub.1                                                                             A.sub.7                                                                             "                                    14      K.sub.2 3            T.sub.1                                                                             A.sub.8                                                                             "                                    15      K.sub.2 3            T.sub.1                                                                             A.sub.9                                                                             "                                    16      K.sub.2 3            T.sub.1                                                                             A.sub.10                                                                            "                                    17      K.sub.2 3            T.sub.1                                                                             A.sub.11                                                                            "                                    18      K.sub.2 3            T.sub.1                                                                             A.sub.12                                                                            "                                    19      K.sub.2 3            T.sub.1                                                                             A.sub.13                                                                            "                                    20      K.sub.2 3            T.sub.1                                                                             A.sub.14                                                                            "                                    21      K.sub.2 3            T.sub.8                                                                             A.sub.14                                                                            "                                    22      K.sub.2 3            T.sub.8                                                                             A.sub.1                                                                             "                                    23      K.sub.2 3            T.sub.8                                                                             A.sub.9                                                                             "                                    24      K.sub.2 3            T.sub.8                                                                             A.sub.10                                                                            "                                    25      K.sub.2 3            T.sub.8                                                                             A.sub.11                                                                            "                                    26      K.sub.2 3            T.sub.8                                                                             A.sub.12                                                                            "                                    27      K.sub.2 4            T.sub.1                                                                             A.sub.1                                                                             "                                    28      K.sub.2 4            T.sub.2                                                                             A.sub.3                                                                             "                                    29      K.sub.2 4            T.sub.4                                                                             A.sub.3                                                                             "                                    30      K.sub.2 4            T.sub.7                                                                             A.sub.3                                                                             "                                    31      K.sub.2 4            T.sub.1                                                                             A.sub.9                                                                             "                                    32      K.sub.2 4            T.sub.1                                                                             A.sub.10                                                                            "                                    33      K.sub.2 4            T.sub.1                                                                             A.sub.11                                                                            "                                    34      K.sub.2 4            T.sub.1                                                                             A.sub.12                                                                            "                                    35      K.sub.2 4            T.sub.1                                                                             A.sub.14                                                                            "                                    36      K.sub.2 4            T.sub.8                                                                             A.sub.11                                                                            "                                    37      K.sub.2 4            T.sub.8                                                                             A.sub.12                                                                            "                                    38      K.sub.3 3            T.sub.1                                                                             A.sub.1                                                                             "                                    39      K.sub.3 3            T.sub.1                                                                             A.sub.2                                                                             "                                    40      K.sub.3 3            T.sub.1                                                                             A.sub.3                                                                             "                                    41      K.sub.3 3            T.sub.3                                                                             A.sub.3                                                                             "                                    42      K.sub.3 3            T.sub.5                                                                             A.sub.3                                                                             "                                    43      K.sub.3 3            T.sub.6                                                                             A.sub.3                                                                             "                                    44      K.sub.3 3            T.sub.1                                                                             A.sub.9                                                                             "                                    45      K.sub.3 3            T.sub.1                                                                             A.sub.10                                                                            "                                    46      K.sub.3 3            T.sub.1                                                                             A.sub.1                                                                             "                                    47      K.sub.3 3            T.sub.1                                                                             A.sub.12                                                                            "                                    48      K.sub.3 3            T.sub.1                                                                             A.sub.13                                                                            "                                    49      K.sub.3 3            T.sub.1                                                                             A.sub.14                                                                            "                                    50      K.sub.3 3            T.sub.8                                                                             A.sub.14                                                                            "                                    51      K.sub.3 3            T.sub.8                                                                             A.sub.1                                                                             "                                    52      K.sub.3 3            T.sub.8                                                                             A.sub.9                                                                             "                                    53      K.sub.3 3            T.sub.8                                                                             A.sub.10                                                                            "                                    54      K.sub.3 3            T.sub.8                                                                             A.sub.11                                                                            "                                    55      K.sub.3 3            T.sub.8                                                                             A.sub.12                                                                            "                                    56      K.sub.3 4            T.sub.1                                                                             A.sub.1                                                                             "                                    57      K.sub.3 4            T.sub.1                                                                             A.sub.3                                                                             "                                    58      K.sub.3 4            T.sub.5                                                                             A.sub.3                                                                             "                                    59      K.sub.3 4            T.sub.1                                                                             A.sub.9                                                                             "                                    60      K.sub.3 4            T.sub.1                                                                             A.sub.12                                                                            "                                    61      K.sub.3 4            T.sub.1                                                                             A.sub.14                                                                            "                                    62      K.sub.3 4            T.sub.8                                                                             A.sub.14                                                                            "                                    63      K.sub.3 4            T.sub.8                                                                             A.sub.10                                                                            "                                    64      K.sub.3 4            T.sub.8                                                                             A.sub.12                                                                            "                                    65      K.sub.1 3            T.sub.1                                                                             A.sub.1                                                                             "                                    66      K.sub.1 3            T.sub.1                                                                             A.sub.3                                                                             "                                    67      K.sub.1 3            T.sub.5                                                                             A.sub.3                                                                             "                                    68      K.sub.1 3            T.sub.4                                                                             A.sub.3                                                                             "                                    69      K.sub.1 3            T.sub.5                                                                             A.sub.3                                                                             "                                    70      K.sub.1 3            T.sub.6                                                                             A.sub.3                                                                             "                                    71      K.sub.1 3            T.sub.7                                                                             A.sub.3                                                                             "                                    72      K.sub.1 3            T.sub.1                                                                             A.sub.4                                                                             "                                    73      K.sub.1 3            T.sub.1                                                                             A.sub.5                                                                             "                                    74      K.sub.1 3            T.sub.1                                                                             A.sub.6                                                                             "                                    75      K.sub.1 3            T.sub.1                                                                             A.sub.7                                                                             "                                    76      K.sub.1 3            T.sub.1                                                                             A.sub.8                                                                             "                                    77      K.sub.1 3            T.sub.1                                                                             A.sub.9                                                                             "                                    78      K.sub.1 3            T.sub.1                                                                             A.sub.10                                                                            "                                    79      K.sub.1 3            T.sub.1                                                                             A.sub.11                                                                            "                                    80      K.sub.1 3            T.sub.1                                                                             A.sub.12                                                                            "                                    81      K.sub.1 3            T.sub.1                                                                             A.sub.13                                                                            "                                    82      K.sub.1 3            T.sub.1                                                                             A.sub.4                                                                             "                                    83      K.sub.1 3            T.sub.8                                                                             A.sub.14                                                                            "                                    84      K.sub.1 3            T.sub.8                                                                             A.sub.3                                                                             "                                    85      K.sub.1 3            T.sub.8                                                                             A.sub.1                                                                             "                                    86      K.sub.1 3            T.sub.8                                                                             A.sub.9                                                                             "                                    87      K.sub.1 3            T.sub.8                                                                             A.sub.10                                                                            "                                    88      K.sub.1 3            T.sub.8                                                                             A.sub.11                                                                            "                                    89      K.sub.1 3            T.sub.8                                                                             A.sub.12                                                                            "                                    90      K.sub.1 3            T.sub.8                                                                             A.sub.6                                                                             "                                    91      K.sub.1 4            T.sub.1                                                                             A.sub.1                                                                             "                                    92      K.sub.1 4            T.sub.2                                                                             A.sub.3                                                                             "                                    93      K.sub.1 4            T.sub.3                                                                             A.sub.3                                                                             "                                    94      K.sub.1 4            T.sub.1                                                                             A.sub.8                                                                             "                                    95      K.sub.1 4            T.sub.1                                                                             A.sub.10                                                                            "                                    96      K.sub.1 4            T.sub.1                                                                             A.sub.12                                                                            "                                    97      K.sub.1 4            T.sub.1                                                                             A.sub.13                                                                            "                                    98      K.sub.1 4            T.sub.8                                                                             A.sub.3                                                                             "                                    99      K.sub.1 4            T.sub.8                                                                             A.sub.1                                                                             "                                    100     K.sub.1 4            T.sub.8                                                                             A.sub.10                                                                            "                                    101     K.sub.1 4            T.sub.8                                                                             A.sub.12                                                                            "                                    102     K.sub.1 3            T.sub.1                                                                             A.sub.7                                                                             X.sub.11                             103     K.sub.1 4            T.sub.1                                                                             A.sub.8                                                                             "                                    104     K.sub.1 3            T.sub.4                                                                             A.sub.3                                                                             "                                    105     K.sub.2 3            T.sub.1                                                                             A.sub.1                                                                             "                                    106     K.sub.2 3            T.sub.1                                                                             A.sub.10                                                                            "                                    107     K.sub.2 3            T.sub.1                                                                             A.sub.12                                                                            "                                    108     K.sub.2 3            T.sub.1                                                                             A.sub.14                                                                            "                                    109     K.sub.2 3            T.sub.8                                                                             A.sub.14                                                                            "                                    110     K.sub.3 3            T.sub.1                                                                             A.sub.1                                                                             "                                    111     K.sub.3 3            T.sub.8                                                                             A.sub.12                                                                            "                                    112     K.sub.1 3            T.sub.1                                                                             A.sub.3                                                                             X.sub.2 '                            113     K.sub.1 4            T.sub.1                                                                             A.sub.3                                                                             "                                    114     K.sub.1 3            T.sub.4                                                                             A.sub.3                                                                             "                                    115     K.sub.3 3            T.sub.1                                                                             A.sub.1                                                                             "                                    116     K.sub.3 3            T.sub.1                                                                             A.sub.10                                                                            "                                    117     K.sub.3 3            T.sub.1                                                                             A.sub.12                                                                            "                                    118     K.sub.3 3            T.sub.1                                                                             A.sub.14                                                                            "                                    119     K.sub.3 3            T.sub.8                                                                             A.sub.12                                                                            "                                    120     K.sub.2 3            T.sub.1                                                                             A.sub.1                                                                             "                                    121     K.sub.2 3            T.sub.8                                                                             A.sub.12                                                                            "                                    122     K.sub.1 3            T.sub.1                                                                             A.sub.3                                                                             X.sub.2 "                            123     K.sub.2 3            T.sub.1                                                                             A.sub.1                                                                             "                                    124     K.sub.3 3            T.sub.1                                                                             A.sub.1                                                                             "                                    125     K.sub.2 3            T.sub.8                                                                             A.sub.12                                                                            "                                    126     K.sub.3 3            T.sub.8                                                                             A.sub.12                                                                            "                                    127     K.sub.1 3            T.sub.1                                                                             A.sub.3                                                                             "                                    128     K.sub.1 3            T.sub.1                                                                             A.sub.3                                                                             X.sub.21 '                           129     K.sub.1 3            T.sub.1                                                                             A.sub.3                                                                             X.sub.19 '                           130     K.sub.1 3            T.sub.1                                                                             A.sub.3                                                                             X.sub.67 '                           131     K.sub.1 3            T.sub.1                                                                             A.sub.3                                                                             X.sub.68 '                           132     K.sub.1 3            T.sub.1                                                                             A.sub.3                                                                             X.sub.72                             133     K.sub.2 3            T.sub.1                                                                             A.sub.1                                                                             X.sub.67 '                           134     K.sub.3 3            T.sub.1                                                                             A.sub.1                                                                             X.sub.68 '                           135     K.sub.3 3            T.sub.8                                                                             A.sub.12                                                                            X.sub.67 '                           136     K.sub.3 3            T.sub.8                                                                             A.sub.12                                                                            X.sub.68 '                           137     K.sub.2 3            T.sub.8                                                                             A.sub.12                                                                            X.sub.72                             138     K.sub.2 4            T.sub.1                                                                             A.sub.1                                                                             X.sub.11                             139     K.sub.2 3            T.sub.1                                                                             A.sub.1                                                                             "                                    140     K.sub.2 4            T.sub.1                                                                             A.sub.1                                                                             X.sub.34 '                           141     K.sub.2 3            T.sub.1                                                                             A.sub.1                                                                             "                                    142     K.sub.2 4            T.sub.1                                                                             A.sub.1                                                                             X.sub.2 "                            143     K.sub.2 3            T.sub.1                                                                             A.sub.1                                                                             "                                    144     K.sub.2 4            T.sub.1                                                                             A.sub.1                                                                             X.sub.2 '                            145     K.sub.2 3            T.sub.1                                                                             A.sub.1                                                                             "                                    ______________________________________                                    

In Examples 131, 134, 136, where X=X₆₈ ', R_(16a) is --NHC₂ H₄ OH.

EXAMPLES 146 TO 181

Compounds of the formula ##STR47## wherein A, K, X and G are defin inTable II and anion A.sup.⊖ is Cl.sup.⊖, may be prepared by a methodanalogous to that of Example 1 from appropriate starting materials.

                  TABLE II                                                        ______________________________________                                        EX.             Position of azo                                               No.       K     group on Ring G                                                                              A      X                                       ______________________________________                                        146       K.sub.2                                                                             3              A.sub.15                                                                             X.sub.34 '                              147       K.sub.2                                                                             3              A.sub.10                                                                             "                                       148       K.sub.2                                                                             3              A.sub.9                                                                              "                                       149       K.sub.2                                                                             3              A.sub.11                                                                             "                                       150       K.sub.2                                                                             3              A.sub.12                                                                             "                                       151       K.sub.2                                                                             4              A.sub.11                                                                             "                                       152       K.sub.2                                                                             4              A.sub.12                                                                             "                                       153       K.sub.3                                                                             3              A.sub.10                                                                             "                                       154       K.sub.3                                                                             3              A.sub.9                                                                              "                                       155       K.sub.3                                                                             3              A.sub.11                                                                             "                                       156       K.sub.3                                                                             3              A.sub.12                                                                             "                                       157       K.sub.3                                                                             3              A.sub.15                                                                             "                                       158       K.sub.3                                                                             4              A.sub.9                                                                              "                                       159       K.sub.3                                                                             4              A.sub.11                                                                             "                                       160       K.sub.3                                                                             4              A.sub.12                                                                             "                                       161       K.sub.1                                                                             3              A.sub.10                                                                             "                                       162       K.sub.1                                                                             3              A.sub.9                                                                              "                                       163       K.sub.1                                                                             3              A.sub.11                                                                             "                                       164       K.sub.1                                                                             3              A.sub.12                                                                             "                                       165       K.sub.1                                                                             3              A.sub.15                                                                             "                                       166       K.sub.1                                                                             3              A.sub.7                                                                              "                                       167       K.sub.1                                                                             4              A.sub.10                                                                             "                                       168       K.sub.1                                                                             4              A.sub.11                                                                             "                                       169       K.sub.1                                                                             4              A.sub.15                                                                             "                                       170       K.sub.2                                                                             3              A.sub.10                                                                             X.sub.11                                171       K.sub.2                                                                             3              A.sub.12                                                                             "                                       172       K.sub.3                                                                             3              A.sub.12                                                                             "                                       173       K.sub.3                                                                             3              A.sub.10                                                                             X.sub.2 '                               174       K.sub.3                                                                             3              A.sub.12                                                                             "                                       175       K.sub.2                                                                             3              A.sub.12                                                                             "                                       176       K.sub.2                                                                             3              A.sub.12                                                                             X.sub.2 "                               177       K.sub.3                                                                             3              A.sub.12                                                                             "                                       178       K.sub.2                                                                             3              A.sub.12                                                                             X.sub.21 '                              179       K.sub.2                                                                             3              A.sub.12                                                                             X.sub.67 '                              180       K.sub.2                                                                             3              A.sub.12                                                                             X.sub.68 '                              181       K.sub.2                                                                             3              A.sub.12                                                                             X.sub.72                                ______________________________________                                    

In Example 180 where X is X₆₈ ' R_(16a) is --NHC₂ H₄ OH.

EXAMPLES 182 TO 202

Compounds of the formula ##STR48## wherein K_(a), K, X and G are definedin Table III below and anion A.sup.⊖ is Cl.sup.⊖ may be prepared by amethod analogous to that of Example 1 from appropriate startingmaterials.

                                      TABLE III                                   __________________________________________________________________________           Position of azo                                                        EX. No.                                                                            K group on Ring G                                                                        K.sub.a               X                                       __________________________________________________________________________    182  K.sub.2                                                                         3                                                                                       ##STR49##            X.sub.34 '                              183  K.sub.2                                                                         4        "                     X.sub.34 '                              184  K.sub.3                                                                         3        "                     X.sub.34 '                              185  K.sub.3                                                                         4        "                     X.sub.34 '                              186  K.sub.1                                                                         3        "                     X.sub.34 '                              187  K.sub.1                                                                         4        "                     X.sub.34 '                              188  K.sub.2                                                                         3        "                     X.sub.11                                189  K.sub.3                                                                         3        "                     X.sub.2 '.sub.                          190  K.sub.2                                                                         3                                                                                       ##STR50##            X.sub.34 '                              191  K.sub.2                                                                         4        "                     X.sub.34 '                              192  K.sub.3                                                                         3        "                     X.sub.34 '                              193  K.sub.1                                                                         3        "                     X.sub.34 '                              194  K.sub.2                                                                         3                                                                                       ##STR51##            X.sub.34 '                              195  K.sub.3                                                                         3        "                     X.sub.34 '                              196  K.sub.1                                                                         3        "                     X.sub.34 '                              197  K.sub.2                                                                         3                                                                                       ##STR52##            X.sub.34 '                              198  K.sub.1                                                                         3        "                     X.sub.34 '                              199  K.sub.2                                                                         3                                                                                       ##STR53##            X.sub.34 '                              200  K.sub.1                                                                         3        "                     X.sub.34 '                              201  K.sub.1                                                                         3                                                                                       ##STR54##            X.sub.34 '                              202  K.sub.1                                                                         3                                                                                       ##STR55##            X.sub.34 '                              __________________________________________________________________________

Dyeing Example A

70 Parts of chemically bleached sulphite cellulose (from pinewood) and30 parts of chemically bleached sulphite cellulose (from birchwood) areground in a Hollander in 2000 parts of water. 0.2 Parts of the dyestuffof in Example 1 are sprinkled into this pulp. After mixing for 20minutes, paper is produced from this pulp. The absorbent paper obtainedin this way is dyed yellow. The waste water is practically colourless.

Dyeing Example B

0.5 Parts of the dyestuff of Example 1 are dissolved in 100 parts of hotwater and cooled to room temperature. This solution is added to 100parts of chemically bleached sulphite cellulose which have been groundin a Hollander with 2000 parts of water. After thorough mixing for 15minutes, sizing takes place. Paper so produced has a yellow shade ofaverage intensity, with good wet fastness.

Dyeing Example C

An absorbent length of unsized paper is drawn through a dyestuffsolution of the following composition at 40° to 50°: 0.5 Parts of thedyestuff of Example 1, 0.5 parts of starch and 99.0 parts of water. Theexcess dyestuff solution is squeezed out through two rollers. The driedlength of paper is dyed yellow with good fastness.

Dyeing Example D

2 Parts of the dyestuff of Example 1 are dissolved at 40° in 4000 partsof softened water. 100 Parts premoistened cotton fabric are entered intothe bath, which is heated for 30 minutes to boiling. The bath is kept atboiling for 1 hour, and the water which evaporates is replaced from timeto time. The dyeing is then removed from the liquor, rinsed with waterand dried. The dyestuff is absorbed practically quantitatively on thefibres; the dye bath is practically colourless. A yellow dyeing isobtained with good light fastness and good wet fastness.

Dyeing Example E

100 Parts of freshly tanned and neutralised chrome grain leather aremilled for 30 minutes in a cask containing a bath of 250 parts of waterat 55° and 1 part of the dyestuff of Example 1 (in acid addition saltform) and are treated for a further 30 minutes in the same bath with 2parts of an anionic fat liquor based on sulphonated train oil. Theleathers are dried and finished in the usual manner. An evenly dyedleather is obtained in yellow shades.

Further low-affinity, vegetable-tanned leathers may be dyed similarly inaccordance with known methods.

Instead of using the compound of Example 1 in any one of Dyeing ExamplesA to E above, an appropriate amount of any one of the compounds ofExample 2 to 202 may be used.

What is claimed is:
 1. A metal-free compound or a 1:1 or 1:2 metalcomplex of the formula ##STR56## wherein each K is independently##STR57## wherein R₃ is hydrogen, C₁₋₄ alkyl, phenyl or benzyl,R₄ isC₁₋₄ alkyl, (C₁₋₄ alkoxy)-carbonyl or --CO--N(R₈)₂, R₅ is amino orhydroxy, R₁₈ is hydrogen, C₁₋₄ alkyl, ##STR58## wherein each R₂₄ isindependently hydrogen, halo, C₁₋₄ alkyl, C₁₋₄ alkoxy, nitro, amino oracetamido, andR₂₅ is hydrogen, --NH--CO--(CH₂)_(a) --Z, --SO₂--NH--(CH₂)_(d) --Z or ##STR59## R₁₉ is hydrogen, C₁₋₆ alkyl, amino,methylamino, phenylamino, (C₁₋₄ alkoxy)C₁₋₄ alkyl, phenyl-(C₁₋₄ alkyl),--(CH₂)_(d) --CN, --(CH₂)_(d) --OH, --(CH₂)_(m) --Z, --(CH₂)_(m) --NR₁₅--CO--(CH₂)_(a) --Z, ##STR60## wherein R₂₇ is hydrogen, amino,methylamino, dimethylamino, diethylamino, acetamido, --NH--CO--(CH₂)_(a)--Z, --(CH₂)_(m) --Z, --SO₂ --NH--(CH₂)_(m) --Z, ##STR61## each R₂₁ isindependently hydrogen, C₁₋₄ alkyl, alkoxy(C₁₋₄ alkyl), 2-hydroxyethylor --(CH₂)_(d) --Z, R₂₂ is --NH--(CH₂)_(m) --Z or nitrophenylamino, R₃₂is hydrogen, --V₁ --Z, C₁₋₄ alkyl or C₁₋₄ hydroxyalkyl, wherein V₁ islinear C₁₋₄ alkylene, R₃₃ is hydrogen, C₁₋₄ alkyl, (C₁₋₄alkyl)carbonylamino or --NH--CO--V₁ --Z, wherein V₁ is linear C₁₋₄alkylene, T' is hydrogen, cyano, carbamoyl or ##STR62## wherein each R₁₀' is independently hydrogen, methyl, amino, dimethylamino or carbamoyl,each V is independently linear C₁₋₁₂ -alkylene; linear alkylene having amaximum of 12 carbon atoms interrupted by 1 or 2 members selected fromthe group consisting of --S--, --O-- and --NR₈ --; C₃₋₁₂ -alkenylene oralkenylene having a maximum of 12 carbon atoms interrupted by 1 or 2members selected from the group consisting of --S--, --O-- and --NR₈ --,V₁ is linear C₁₋₄ alkylene, Z is --N(R₂₉)₂ or --N.sup.⊕ (R₃₀)₂ R₃₁A.sup.⊖, whereineach R₂₉ is independently hydrogen; C₁₋₄ alkyl;phenyl(C₁₋₄ -alkyl) or C₂₋₄ alkyl mono-substituted by hydroxy, halo orcyano or --N(R₂₉)₂ is morpholino, piperidino, pyrrolidino, piperazino orN-methylpiperazino, each R₃₀ is independently C₁₋₄ alkyl, phenyl(C₁₋₄-alkyl) or C₂₋₄ alkyl monosubstituted by hydroxy, halo or cyano, and R₃₁is C₁₋₄ alkyl or phenyl(C₁₋₄ -alkyl) or --N.sup.⊕ (R₃₀)₂ R₃₁ A.sup.⊖ ispyridinium A.sup.⊖, picolinium A.sup.⊖, lutidinium A.sup.⊖, ##STR63##wherein R₃₁ is C₁₋₄ -alkyl or phenyl(C₁₋₄ -alkyl), each Z₁ isindependently --N(R₂₉)₂, --N.sup.⊕ (R₃₀)₂ R₃₁ A.sup.⊖ or hydroxy,wherein R₂₉, R₃₀ and R₃₁ are as defined above, and each n isindependently 1, 2, 3 or 4, each K₁ is independently ##STR64## whereinR₃ is hydrogen, C₁₋₄ alkyl, phenyl or benzyl,R₄ is C₁₋₄ alkyl, (C₁₋₄alkoxy)-carbonyl or --CO--N(R₈)₂, R₅ is amino or hydroxy, R_(5a) ishydroxy, T is hydrogen, cyano, ##STR65## or (C₁₋₄ alkyl)carbonyl,wherein R₇ is C₁₋₄ alkyl,each R₁₀ is independently hydrogen, C₁₋₄ alkyl,--N(R₁₂)₂ or --CO--N(R₁₂)₂, wherein R₁₂ is as defined below, each R₁₂ isindependently hydrogen, cyclohexyl, C₁₋₄ alkyl or C₁₋₄ hydroxyalkyl,Z_(a) is --S--, --O-- or --NR₈ --, and the * denotes the atom attachedto Ring B, each R₁ is independently hydrogen, halo, hydroxy, C₁₋₄ alkoxyor C₁₋₄ alkyl, or R₁ and R₅, located on rings attached to the same azoradical, are --O--Me--NH-- or --O--Me--O--, wherein Me is a 1:1 or 1:2metal complex-forming metal ion, or R₁ and R_(5a), located on ringsattached to the same azo radical, are --O--Me--O--, wherein Me is asdefined above, each R₂ is independently hydrogen, halo, C₁₋₄ alkyl orC₁₋₄ alkoxy, X is a direct bond, linear or branched C₁₋₄ alkylene,##STR66## wherein R₁₄ is halo, C₁₋₄ alkyl or C₁₋₄ alkoxy,each R₁₅ isindependently hydrogen or C₁₋₄ alkyl, R₁₆ is halo, hydroxy, amino,--NR₃₄ R₃₅, N,N-di-(2-hydroxyethyl)amino, --NR₃₄ --A₁ --NR₃₄ R₃₅,##STR67## wherein A₁ is linear or branched C₁₋₄ -alkylene,each R₃₄ isindependently hydrogen or C₁₋₄ alkyl, and R₃₅ is C₁₋₄ alkyl or C₁₋₄hydroxyalkyl, each R₁₇ is independently linear or branched C₁₋₄alkylene, and each g is independently 1, 2, 3 or 4, with the provisothat when at least one R₁ is other than hydrogen, X is a direct bond,linear or branched C₁₋₄ alkylene, ##STR68## wherein R₁₅ -R₁₇ are asdefined above, and each q is independently 0 or 1, whereineach R₈ isindependently hydrogen or C₁₋₄ alkyl, each R₁₅ is independently hydrogenor C₁₋₄ alkyl, each R₂₈ is independently halo, hydroxy, amino, --NH--C₂H₄ OH, --N(C₂ H₄ OH)₂, --NH--(CH₂)_(m) --Z, --NH--(CH₂)_(d) --CN,--NH--(CH₂)_(d) --O--C₁₋₄ alkyl, morpholino, ##STR69## wherein R₁₅ and Zare as defined above, andd and m are as defined below, each Z isindependently as defined above, each A.sup.⊖ is independently anon-chromophoric anion, each a is independently 1 or 2, each d isindependently 2 or 3, and each m is independently 1, 2, 3, 4, 5 or6,with the provisos that (i) the compound of Formula I has at least twobasic water-solubilizing groups, and (ii) each end of X is in the 3- or4-position of the Ring A to which it is attached.
 2. A metal-freecompound or a 1:1 or 1:2 metal complex according to claim 1 whereineachMe is independently iron, copper, cobalt, nickel, manganese or chromiumin a 1:1 metal complex and cobalt, chromium, nickel or iron in a 1:2metal complex.
 3. A metal-free compound according to claim
 2. 4. A 1:1or 1:2 metal complex according to claim
 2. 5. A metal-free compound or a1:1 or 1:2 metal complex according to claim 2 whereineach R₁₂ isindependently hydrogen or C₁₋₄ alkyl, R₁₆ is chloro, hydroxy, amino,2-hydroxyethylamino, di-(2-hydroxyethyl)amino,3-diethylaminopropylamino, N-methyl-N-phenylamino orN-cyclohexyl-N-methylamino, each R₁₇ is independently --(CH₂)_(d) --,any (C₁₋₄ alkoxy)C₁₋₄ alkyl as R₁₉ or alkoxy-(C₁₋₄ alkyl) as R₂₁ is3-methoxypropyl, any m in R₂₂, R₂₇ or R₂₈ is 2 or 3, R₃₂ is hydrogen,--(CH₂)_(d) --Z or C₁₋₄ alkyl, each V is independently --(CH₂)_(b) --,wherein b is 2, 3, 4, 5 or 6, each V₁ is independently --(CH₂)_(d) --,each g is independently 2, 3 or 4, and each n is
 2. 6. A metal-freecompound or a 1:1 or 1:2 metal complex according to claim 1 having theformula ##STR70## wherein each K' is independently K, where K is asdefined in claim 1,each K₁ ' is independently ##STR71## wherein R₃ ' ismethyl, ethyl or phenyl,R₅ is amino or hydroxy, R_(5a) is hydroxy, T' ishydrogen, cyano, carbamoyl or ##STR72## wherein each R₁₀ ' isindependently hydrogen, methyl, amino, dimethylamino or carbamoyl, andthe * denotes the atom attached to Ring B, each R₁ ' is independentlyhydrogen, chloro, methyl, methoxy or hydroxy, or A.sup.⊖ is anon-chromophoric anion, R₁ ' and R₅, located on rings attached to thesame azo radical, are --O--Me--NH-- or --O--Me--O--, wherein Me is a 1:1or 1:2 metal complex-forming metal ion, or R₁ ' and R_(5a), located onrings attached to the same azo radical, are --O--Me--O--, wherein Me isas defined above, and X' is a direct bond, --CH₂ --, --(CH₂)₂ --,--(CH₂)₃ --, --(CH₂)₄ --, --S--, --O--, --CH═CH--, --NH--, --NHCO--,##STR73## wherein R_(14a) is hydrogen, chloro, methyl or methoxy,R_(16a)is chloro, hydroxy, amino, 2-hydroxyethylamino,di-(2-hydroxyethyl)amino, 3-diethylaminopropylamino,N-methyl-N-phenylamino or N-cyclohexyl-N-methylamino, R₁₇ is linear orbranched C₁₋₄ alkylene, and g is 1, 2, 3 or 4, with the proviso thatwhen at least one R₁ ' is other than hydrogen, X' is a direct bond,--CH₂ --, --(CH₂)₂ --, ##STR74## wherein R_(16a) is as defined above,with the provisos that (i) the compound of Formula I' has at least twobasic water-solubilizing groups, (ii) each end of X' is in the 3- or4-position of the Ring A to which it is attached, and (iii) each azoradical attached to a Ring B is in the 3- or 4-position thereof.
 7. Ametal-free compound or a 1:1 or 1:2 metal complex according to claim 6whereinR₁₇ is --(CH₂)_(d) --, any (C₁₋₄ alkoxy)C₁₋₄ alkyl as R₁₉ or(alkoxy)C₁₋₄ -alkyl as R₂₁ is 3-methoxypropyl, R₃₂ is hydrogen,--(CH₂)_(d) --Z or C₁₋₄ alkyl, each V is independently --(CH₂)_(b) --,wherein b is 2, 3, 4, 5 or 6, each V₁ is independently --(CH₂)_(d) --,each Me is independently iron, copper, cobalt, nickel, manganese orchromium in a 1:1 metal complex and cobalt, chromium, nickel or iron ina 1:2 metal complex, independently g is independently 2, 3 or 4, any min R₂₂, R₂₇ or R₂₈ is 2 or 3, and each n is
 2. 8. A metal-free compoundaccording to claim
 7. 9. A 1:1 or 1:2 metal complex according to claim7.
 10. A metal-free compound or a 1:1 or 1:2 metal complex according toclaim 6 having the formula ##STR75## wherein each K" is independently##STR76## wherein R₅ is amino or hydroxy,R₁₈ ' is hydrogen, ##STR77##wherein each R₂₄ ' is independently hydrogen, chloro, methyl, methoxy oracetamido, andR₂₅ ' is hydrogen, --NH--CO--CH₂ --Z', --SO₂--NH--(CH₂)_(d) --Z' or ##STR78## R₁₉ ' is hydrogen, methyl, ethyl,benzyl, 2-phenylethyl, phenylamino, 2-cyanoethyl, 2hydroxyethyl,3-methoxypropyl, --(CH₂)_(d) --Z', ##STR79## or --(CH₂)_(d)--NH--CO--CH₂ --Z', wherein R₂₇ ' is hydrogen, amino, dimethylamino,diethylamino, acetamido, --NH--CO--CH₂ --Z', --(CH₂)_(d) --Z', --SO₂--NH--(CH₂)_(d) --Z' or ##STR80## each R₂₁ ' is independently hydrogen,methyl, ethyl, 2-hydroxyethyl, 3-methoxypropyl or --(CH₂)_(d) --Z', R₂₂' is --NH'(CH₂)_(d) --Z' or nitrophenylamino, R₃₃ ' is hydrogen, methyl,acetamido, propionamido or --NH--CO--(CH₂)_(d) --Z', T" is cyano or##STR81## wherein R₁₀ " is hydrogen, methyl or amino, each V' isindependently --(CH₂)_(b) --, wherein b is 2, 3, 4, 5 or 6, Z' is--N(R₂₉ ')₂ or --N.sup.⊕ (R₃₀ ')₂ R₃₁ ' A.sup.⊖, whereineach R₂₉ ' isindependently hydrogen, methyl or ethyl, or --N(R₂₉ ') is morpholino,piperidino, piperazino or N-methylpiperazino, each R₃₀ ' isindependently methyl or ethyl, and R₃₁ ' is methyl, ethyl or benzyl, or--N.sup.⊕ (R₃₀ ')₂ R₃₁ ' A.sup.⊖ is pyridinium A.sup.⊖, α-picoliniumA.sup.⊖ or β-picolinium A.sup.⊖, and each Z₁ ' is independently --N(R₂₉')₂ or hydroxy, wherein R₂₉ ' is as defined above, wherein each R₁₅ ' isindependently hydrogen or methyl, each R₂₈ ' is independently chloro,hydroxy, amino, phenylamino, cyclohexylamino, --NH--C₂ H₄ OH, --N(C₂ H₄OH)₂, 2-cyanoethylamino, 3-methoxypropylamino or --NH--(CH₂)_(d) --Z',whereinZ' is as defined above, and d is as defined below, each Z' isindependently as defined above, and each d is independently 2 or 3, eachK₁ " is independently ##STR82## wherein R₅ is amino or hydroxy,R_(5a) ishydroxy, T" is as defined above, and the * denotes the atom attached toRing B, each R₁ ' is independently hydrogen, chloro, methyl, methoxy orhydroxy, or R₁ ' and R₅, located on rings attached to the same azoradical, are --O--Me₁ --NH-- or --O--Me₁ --O--, wherein Me₁ is copper ina 1:1 metal complex and cobalt, chromium or iron in a 1:2 metal complex,or R₁ ' and R_(5a), located on rings attached to the same azo radical,are --O--Me₁ --O--, wherein Me₁ is as defined above, and X" is a directbond, --CH₂ --, --(CH₂)₂ --, --NH--CO--, ##STR83## wherein R_(16a) ischloro, hydroxy, amino, 2-hydroxyethylamino, di-(2-hydroxyethyl)amino,3-diethylaminopropylamino, N-methyl-N-phenylamino orN-cyclohexyl-N-methylamino, andR₁₇ is linear or branched C₁₋₄ alkylene,with the proviso that when at least one R₁ ' is other than hydrogen, X"is a direct bond,wherein each A.sup.⊖ is independently anon-chromophoric anion, with the provisos that (i) the compound ofFormula I" has at least two basic water-solubilizing groups, and (ii)each azo radical attached to a Ring B in the 3- or 4-position thereof.11. A metal-free compound according to claim
 10. 12. A metal-freecompound according to claim 11 whereinthe two K"'s are identical, thetwo K₁ "'s are identical, the two R₁ ''s are identical, and each azoradical attached to a Ring B is in the 3-position thereof or each azoradical attached to a Ring B is in the 4-position thereof.
 13. Ametal-free compound according to claim 10 having the formula ##STR84##14. A 1:1 or 1:2 metal complex according to claim
 10. 15. A 1:1 or 1:2metal complex according to claim 14 whereinthe two K"'s are identical,the two K₁ "'s are identical, the two R₁ ''s are identical, and each azoradical attached to a Ring B is in the 3-position thereof or each azoradical attached to a Ring B is in the 4-position thereof.